CN113151676A

CN113151676A - Retrieve device of tombarthite in follow tombarthite waste material

Info

Publication number: CN113151676A
Application number: CN202110434374.4A
Authority: CN
Inventors: 黄玉春; 丁凡
Original assignee: Zehao High Purity Metal Co ltd; Beijing Yaozhi Environmental Protection Technology Co ltd
Current assignee: Zehao High Purity Metal Co ltd; Beijing Yaozhi Environmental Protection Technology Co ltd
Priority date: 2021-04-22
Filing date: 2021-04-22
Publication date: 2021-07-23

Abstract

The invention discloses a device for recovering rare earth from rare earth waste, which comprises a reaction tank, a solid-liquid separation device, an ion exchange electrolytic membrane device, an ion exchange impurity removal system, a stirring tank and a molecular recognition ion exchange system, wherein the rare earth waste and a dissolving agent are added into the reaction tank for dissolving and leaching to form a rare earth dissolved mixed solution, the rare earth dissolved mixed solution is sent into the solid-liquid separation device for separating a rare earth dissolved solution, and the rare earth dissolved mixed solution is transferred into the ion exchange electrolytic membrane device for separating a recycled acid and a deacidified rare earth solution; the deacidified rare earth solution enters an ion exchange impurity removal system to adsorb impurities and separate the impurity-removed rare earth solution; and (3) feeding the rare earth solution after impurity removal into a stirring tank, adding a molecular recognition reagent to form a rare earth complex solution, feeding the rare earth complex solution into a molecular recognition ion exchange system for ion exchange, and separating a rare earth product. The invention has simple structure, can recycle valuable metals and rare earth elements on site, can reduce waste transfer and transportation, recycles and recycles waste materials, does not generate environmental pollution, and is suitable for industrial continuous production.

Description

Retrieve device of tombarthite in follow tombarthite waste material

Technical Field

The invention relates to a rare earth recovery device, in particular to a device for recovering rare earth from rare earth waste.

Background

Rare earth elements are widely used for manufacturing new functional materials, and due to the factors of production processes, large or small waste materials are generated in the production and use processes. Only the leftover waste material produced by cutting the permanent magnet neodymium iron boron produced by production and processing in China every year, namely the so-called neodymium iron boron waste material, is as high as 1-2 ten thousand tons. Other electrolytic wastes, such as those produced by electrolysis of rare earth metals, are several tens of thousands of tons per year. Therefore, it is more necessary to recover precious rare earth elements from rare earth scrap. However, due to the limitations of the separation and purification production and application level of rare earth elements, the waste materials can only be transported to a special rare earth processing plant for extraction and recovery, and the transportation of industrial waste materials often has risks and affects the environment. Moreover, rare earth processing enterprises need to bear the cost of waste transportation and processing, and on-site processing and resource recycling become important projects of the enterprises at present.

With the progress of science and technology, rare earth elements are used for manufacturing high-tech materials in large quantity, and although rare earth recycling non-renewable precious resources from scrapped functional materials has developed into a special industry, the technical process of recycling production needs to be perfected, and the processes of low energy consumption, no secondary pollutants and resource application are more important improvement links. The general rare earth waste recovery production process comprises crushing, roasting, acid dissolution, extraction separation, precipitation and final roasting, and the produced pollutants are huge and have profound influence on the environment. Because the waste materials produced by each manufacturing enterprise are different, the waste material recovery and production process becomes extremely complicated, and the used pharmaceutical quantity is also large. The stability of the original waste can be ensured by on-site treatment and recovery, and the quality of the rare earth recovered by enterprises according to the requirements of the enterprises can be adjusted, thereby reducing resource misuse.

Due to the diversity and complexity of rare earth wastes, the differences of material elements contained in various rare earth wastes are large, so that several treatment steps are required for treatment, effective and complete extraction rate is achieved, and the wastes containing rare earth elements are decomposed in a physical and chemical manner. In general, the rare earth scrap processing flow comprises the following main steps: physical treatment, chemical treatment, separation and purification and precipitation reduction. Because the properties of the rare earth elements are very similar, separation and purification are most important in the treatment process of rare earth waste materials.

The physical treatment process is respectively suitable for different types of rare earth wastes, including grinding, screening, gravity separation, magnetic separation, froth flotation, high-temperature roasting and the like. The chemical treatment step is to convert the rare earth waste into carbonate or chloride by a hydrometallurgical process, in which rare earth elements are mixed in a strong acid or alkali to produce a chemical reaction and converted into a solution in a soluble salt or ionic state. However, the leaching step is less selective and a large amount of other impurity elements are also dissolved during leaching. Another difficulty is that the waste material from various rare earth metal processing plants has widely varying material distribution, concentration, etc. and therefore requires additional separation and purification steps to ensure the purity of the rare earth elements produced is satisfactory for further use.

As described above, the conventional rare earth separation method mainly comprises selective chemical precipitation, for example, adjusting different pH values to precipitate different rare earth elements or impurities, as described in patent CN1119216A, the acid-dissolved rare earth solution is precipitated by a double salt precipitation method to obtain the desired rare earth elements, and then the desired rare earth elements are extracted and purified by a conversion method.

Solvent extraction (or liquid-liquid extraction) is a set of commonly used rare earth separation technology, the operation flow is specifically to grind and roast rare earth waste, then separate the rare earth through solvent extraction, and the industry mostly uses an extractant which takes an acidic phosphorus type extractant P507 or P204 as a main part to separate rare earth elements. In order to improve the separation coefficient and the extraction rate, in the rare earth extraction process, ammonia water or alkaline substances such as sodium hydroxide and calcium hydroxide are generally adopted to carry out saponification treatment on acidic extracting agents such as P507, wherein the saponification reaction is an exchange reaction between ammonium ions (or sodium ions, calcium ions and the like) and hydrogen ions in the acidic extracting agents, and the ammonium ions are introduced into the saponified extracting agents; for the extraction process of the rare earth, the ammonium ions in the saponification extracting agent and the rare earth ions are subjected to exchange reaction, so that the acidity of the extraction process can be kept unchanged, and the extraction reaction can be continuously carried out. Along with the extraction reaction, the exchanged ammonium ions (or sodium ions, calcium ions and the like) are gradually accumulated in the water phase to generate wastewater containing ammonia nitrogen or wastewater containing sodium ions, calcium ions and the like to be treated. In recent years, technologies for separating rare earth elements by saponification-free extraction (such as patents CN104532021B, CN101319275A, and CN 102618736A) have been developed, and the rare earth elements in the system are separated without using acidic extractant such as P507, so that ammonia nitrogen wastewater is not generated, and cations and anions in the extractant molecules in the system react with rare earth ions to form neutral complex molecules, thereby improving the benefit of separation coefficient between rare earth elements. The rare earth elements are extracted, separated, extracted, washed and roasted to be oxidized into rare earth oxides.

The novel rare earth element separation and purification method comprises ion exchange and solid phase extraction, the ion exchange chromatography is needed for rare earth separation and purification before the solvent extraction is not adopted in the early stage, and the ion exchange method can be used for obtaining the rare earth element with the purity higher than 99.9999%; however, its large-scale application is limited by high cost. At present, the function of the ion exchange resin is improved, the production cost is reduced, and the research for separating the rare earth elements is increased continuously, for example, as described in patent CN104593591B, the rare earth elements are separated by adopting the ion exchange resin method, and the problem of environmental pollution caused by saponification is solved.

The research on another solid phase extraction method similar to the ion exchange method is also in progress, and as described in patent US20170101698a1, the solid phase extraction method is a sample pretreatment technology developed from the mid-eighties. Developed by combining liquid-solid extraction and liquid chromatography techniques. The method is mainly used for separating, purifying and enriching samples. The solid phase extraction method is mainly applied to detection in the early days, and aims to reduce the matrix interference of a detected sample and improve the detection sensitivity. The separation principle of liquid chromatography of selective adsorption and selective elution is utilized. The more common method is to make the liquid sample solution pass through the adsorbent to retain the tested substance, then to select the solvent with proper strength to wash out the impurity, then to use a small amount of solvent to quickly elute the tested substance, thus to achieve the purpose of quick separation, purification and concentration. Interference impurities can be selectively adsorbed, so that the measured substance flows out; or adsorbing impurities and the substance to be detected simultaneously, and then selectively eluting the substance to be detected by using a proper solvent. With the continuous progress of the technology for manufacturing solid phase materials, the rare earth separation and purification has been used. The solid phase extraction method does not need to use a large amount of medicaments, can accurately separate and purify the rare earth elements and has the advantage of high speed.

The organic acid dissolution separation method is a method for selectively dissolving rare earth waste by using organic dissolving agents, such as acetic acid, lactic acid and the like, wherein rare earth elements are dissolved, but most of the rare earth elements, such as iron, aluminum and the like, are not dissolved, and as described in patents WO2017/011368Al, WO2016/201558Al and US8734714B2, rare earth is recovered from an organic acid solution in one step by dissolving the organic acid, extracting by using clear water and temperature change. The method has the advantages of short operation flow, simple equipment use, capability of recycling organic acid, small amount of waste water and the like, and is especially suitable for processing rare earth waste with small amount.

The selective precipitation method is suitable for recovering rare earth waste with low requirement on quantity, and is a good method for extracting and recovering rare earth on site by a medium and small manufacturer. Moreover, the recovery rate is low by using a selective precipitation method, and the extraction efficiency is difficult to achieve under the condition of high salinity.

The extraction separation method for separating and extracting rare earth is the most widely adopted method, the selective difference between adjacent elements of liquid-phase extractant is utilized for separating and purifying rare earth elements, the extraction separation method has the greatest advantages that the production output is large, annual treatment of rare earth waste can reach more than ten thousand tons, the used extractant can be recycled, saponification treatment is required during extraction, the consumption of chemical agents is large, the pollution is high, and secondary pollution is caused to the environment. In addition, the extraction separation method has long operation flow, is unfavorable for small and unstable supply, has very large amount of rare earth in the pressure tank and very high capital pressure, requires tens of millions of rare earth in the pressure tank in one production line, and separates some heavy rare earth elements with small amount and high price, thereby greatly burdening enterprises. Even if the rare earth elements are separated by using the saponification-free extraction method as proposed in patent CN104532021B, the loaded organic phase needs to be washed by dilute acid and the loaded organic phase needs to be back-extracted by using acid with higher concentration, which makes the acidity of the back-extraction solution, the washing solution and the blank organic phase after back-extraction very high, especially the acidity of the product at the back-extraction solution outlet higher, which is not beneficial to the treatment or separation of the subsequent product. Therefore, alkaline substances are still consumed in the saponification-free extraction process, and for a blank organic phase, multi-stage water washing is needed to elute a large amount of acid carried in the blank organic phase, so that the blank organic phase can be recycled, and the extraction process is greatly prolonged.

The solid phase extraction method or the ion exchange method is used as a method for removing impurities and separating after acid dissolution of rare earth waste, the method is a simple and environment-friendly quick method for separating and recovering the rare elements, the solid phase extraction method customizes specific adsorbates according to the specific rare earth elements, and the ion exchange resin is a network structure high molecular compound with active groups and has the functions of exchange, selection, adsorption enrichment and catalysis. The resin can selectively adsorb different ions according to different active groups, thereby achieving the purpose of enrichment. It has been published in patents (patent 89101932, patent 85101874, patent CN85101611) that rare earth elements are separated and purified by ion exchange method, and single rare earth product with extremely high purity can be obtained in one step. The prepared rare earth product has high value. However, when the rare earth ions are adsorbed by using the ion exchange resin alone, the yield is low because of the low exchange speed, and the yield is low because of the rare earth separation method in the ion exchange method such as the chromatography method alone, and the yield is difficult to achieve.

The rare earth waste can be selectively dissolved by an organic acid dissolving and separating method, the rare earth can be recovered in one step, and the greatest advantages are short operation process, simple equipment use and the like, but as described in patents WO2017/011368Al, WO2016/201558Al and US8734714B2, the reasons of incomplete rare earth recovery and low recovery rate are that part of rare earth wrapped by iron cannot be leached in an organic acid solution, and the organic acid cannot be applied to rare earth waste which is complexed with rare earth substances such as fluorine.

Disclosure of Invention

The invention aims to provide a device for recovering rare earth from rare earth waste so as to solve the problem of recovering rare earth from rare earth waste.

In order to solve the existing technical problems, the technical scheme adopted by the invention is as follows: a device for recovering rare earth from rare earth waste comprises a reaction tank, a solid-liquid separation device, an ion exchange electrolytic membrane device, an ion exchange impurity removal system, a stirring tank and a molecular recognition ion exchange system, wherein the rare earth waste and a dissolving agent are added into the reaction tank for dissolving and leaching to form a rare earth dissolved mixed solution, the rare earth dissolved mixed solution is sent into the solid-liquid separation device for separating a rare earth dissolved solution, the rare earth dissolved solution is transferred into the ion exchange electrolytic membrane device for separating a recycling acid and a deacidified rare earth solution, and the recycling acid is returned to the reaction tank for recycling; the deacidified rare earth solution enters an ion exchange impurity removal system to adsorb impurities and separate the impurity-removed rare earth solution; feeding the rare earth solution after impurity removal into a stirring tank, adding a molecular recognition reagent, and mixing with the rare earth solution after impurity removal to form a rare earth complex solution; and (4) feeding the rare earth complex solution into a molecular recognition ion exchange system for ion exchange, and separating out rare earth products.

Furthermore, the device also comprises a wastewater treatment system, wherein the wastewater treatment system treats the wastewater separated by the molecular recognition ion exchange system into reuse water, and returns the reuse water to the ion exchange electrolytic membrane equipment to be used for manufacturing reuse acid.

The dissolving agent is divided into an alkaline dissolving agent and an inorganic acid dissolving agent, the alkaline dissolving agent is used for pretreating the rare earth waste, the rare earth waste is pretreated by dissolving the alkaline dissolving agent, then is separated by a solid-liquid separation device and then returns to the reaction tank, and the inorganic acid dissolving agent is added for dissolving and leaching.

Further, in order to help leaching efficiency, the reaction tank of the present invention further comprises a heating device, and the heating of the reaction tank is preferably 5 to 150 degrees when the dissolution leaching is performed.

Further, the heating of the reaction tank of the present invention is more preferably 70 to 80 degrees.

In general, the ion exchange abatement system of the present invention may employ resins of the iminodiacetic acid, phosphoramidate, or 2-aminomethylpyridine type.

Furthermore, after the ion exchange impurity removal system is saturated, desorption agents can be used for desorption, and eluted metals are used for recovery.

Generally, the molecular recognition agent of the present invention is tetraoxetane, tris [ N, N-bis (trimethylsilane) amine ], or other organic complexing agent.

Generally, the dissolving agent of the present invention is hydrochloric acid, sulfuric acid, nitric acid or other inorganic acid, and the acid concentration of the dissolving agent is preferably 5 to 35%.

Generally, the dissolving agent is sodium hydroxide, sodium carbonate, ammonia water, potassium oxide or other inorganic alkali, and the alkali concentration of the dissolving agent is preferably 5-95%.

The present invention relates to a rare earth production method, including grinding rare earth waste material, roasting and oxidizing, feeding the waste material into reaction tank of said equipment, adding inorganic acid to make heating and acid-dissolving, making solid-liquid separation of acid-dissolved leachate, recovering acid by means of ion-exchange electrolytic membrane acid recovery device, removing impurities by means of ion-exchange resin to remove most of impurities except rare earth elements, for example iron and calcium to obtain rare earth-rich solution, adding molecular identification agent according to rare earth element class to make calibration after "molecular identification-ion exchange" (MRIX), then making quick separation by means of selective adsorption or non-adsorption of calibrated rare earth elements by means of ion exchange, using acid-washing to desorb the calibrated rare earth elements adsorbed by ion-exchange resin, and precipitating so as to obtain high-purity rare earth elements.

The invention has simple equipment and small occupied area, has the best benefit on rare earth waste containing a plurality of rare earth elements (such as permanent magnet neodymium iron boron, rare earth metal dissolved salt electrolysis waste and the like), and is suitable for batch production. The ion exchange electrolytic membrane acid recovery device saves the consumption of chemical agents and can reduce pollutants generated in production. The separation and purification technology for extracting rare earth elements without solvent uses corner-type ion exchange resin to remove most impurities after acid dissolution, captures individual rare earth elements through molecular recognition, and finally produces high-purity rare earth elements through ion exchange separation, purification and enrichment in one step. The agent used in the molecular recognition technology of the invention can be customized according to the atomic radius of each rare earth element.

The invention aims at recovering and purifying rare earth materials from rare earth waste materials generated after smelting and processing rare earth, and uses single fixed container equipment to perform the steps of oxidation, dissolution, impurity removal and separation and purification of the rare earth waste materials, thereby comprehensively recovering rare earth waste materials in one step. The invention is an integrally designed and integrally sealed device, which is used for recovering rare earth elements by a simple and convenient method and is matched with molecular recognition and ion exchange to be used as the device for quickly recovering, separating and purifying metals such as neodymium, dysprosium, terbium and cobalt. The invention has simple structure, light equipment, low equipment cost and recycling of medicament, is suitable for being configured on a rare earth processing production line to recover valuable metals and rare earth elements on site, and is suitable for being applied to rare earth metal, neodymium iron boron permanent magnet material processing, rare earth recovery industry and the like. Can reduce waste transfer and transportation, recycles and recycles waste materials, and has obvious economic benefit. No environmental pollution and suitability for industrial continuous production.

Advantageous effects

The invention does not use solvent extraction method for rare earth separation and extraction, reduces the flow, greatly reduces the problem of rare earth source material pressure tank, accelerates the product output, reduces the operating capital pressure problem, can be treated in batch, is quite beneficial to rare earth product production enterprises with single type and stable waste sources, is convenient for solving the waste problem on site, and recycles the rare earth resources. The invention uses common inorganic acid, such as hydrochloric acid, sulfuric acid, etc. as the rare earth waste for dissolution, and can also carry out alkali dissolution pretreatment on the rare earth waste with complex in the same reaction tank in advance, thereby simplifying the process and improving the recovery rate of the rare earth by acid dissolution. The equipment of the invention is provided with an ion exchange electrolytic membrane acid recovery device, so that the acid can be recycled, the use of the medicament is saved, and the generation of pollutants can be reduced. One of the main equipments of the invented device is equipped with ion exchange impurity removal and molecular recognition-ion exchange (MRIX), the ion exchange impurity removal utilizes ion exchange selective exchange tree to remove most of impurities except rare earth elements, such as iron, copper, cobalt and calcium, etc., and the rest rare earth liquid and impurities with small quantity are separated and extracted into high-purity rare earth product by using molecular recognition-ion exchange (MRIX) as rare earth element. The method has the advantages that the separation of a plurality of rare earth elements can be rapidly realized on rare earth waste materials (such as permanent magnet neodymium iron boron, rare earth metal dissolved salt electrolysis waste materials and the like) with a small variety of rare earth elements. Is suitable for on-site waste treatment and recovery, and reduces the pollution to the environment.

Drawings

FIG. 1 is a flow chart of rare earth recovery;

FIG. 2 is a graph comparing atomic radii of rare earth elements;

FIG. 3 shows a molecular structure diagram of a tetraoxetane (DOTA) molecular recognition reagent;

the figure includes: the method comprises the following steps of 1, a heating device 2, a rare earth dissolved mixed solution 3, a reaction tank stirrer 4, a recycled acid 5, a solid-liquid separation device 6, a desorption agent 7 of an ion exchange impurity removal system, a rare earth dissolved solution 8, an ion exchange impurity removal system 9, a reaction tank 10, an impurity-removed rare earth solution 11, a stirring tank stirrer 12, a stirring tank 13, a molecular recognition agent 14, a rare earth complex solution 15, a molecular recognition ion exchange system 16, a desorption agent 17 of the molecular recognition ion exchange system, a rare earth product 18, a wastewater treatment system 19, recycled water 20, ion exchange electrolytic membrane equipment 21, impurities 22, a stirring blade 23, a deacidified rare earth solution 24, rare earth element ions 25, tetraazacyclo 26, rare earth elements 27 and rare earth element atoms 28.

Detailed Description

The present invention is further described in detail below with reference to specific examples so that the advantages and features of the present invention may be more readily understood by those skilled in the art, and thus the scope of the present invention is more clearly defined.

As shown in the attached figure 1, which is a flow chart of the invention for recovering rare earth, the rare earth waste 1 after being ground and roasted and oxidized enters a reaction tank 10, an alkaline dissolving agent such as sodium oxide or sodium carbonate is added for the pre-dissolving treatment or inorganic acid such as hydrochloric acid or sulfuric acid is directly added as the dissolving agent for dissolving and leaching, the reaction tank 10 is heated to 70-80 ℃ by a heating device 2 to help the leaching efficiency, if the rare earth waste 1 can be separated by a solid-liquid separation device 6 after the pre-dissolving treatment, the rare earth waste returns to the reaction tank 10 for the acid dissolving and leaching, and the solid-liquid separation device 6 can be a filter press, a filter or a centrifuge, etc. Dissolving rare earth and partial impurities into a rare earth dissolved mixed solution 3, separating a rare earth dissolved solution 8 from the rare earth dissolved mixed solution 3 by a solid-liquid separation device 6, the rare earth solution 8 is transferred to an ion exchange electrolytic membrane device 21 for acid recovery to reduce the acid concentration of the rare earth solution 8, but also can be recycled to reuse acid 5 and return to the reaction tank 10 for recycling, the deacidified rare earth solution 24 enters an ion exchange impurity removal system 9 to absorb impurities 22 such as copper, cobalt, iron, calcium and the like, the functional group of the resin used by the ion exchange impurity removal system 9 is iminodiacetic acid, aminophosphoric acid or 2-aminomethyl pyridine, the resin can selectively remove some two frames of positive ion metal and three frames of iron ions, and in addition, the resin can be matched with a corner-bonded weak-base ion exchange resin, and (3) removing impurities of negative ions in the water, wherein the rare earth solution 11 which is discharged from the ion exchange impurity removal system 9 and is subjected to impurity removal only contains trace impurities. After the resin of the ion exchange impurity removal system 9 is saturated, desorption agents such as acid, alkali and the like can be used for desorption, and the eluted metal can be recovered.

And (3) carrying out molecular recognition-ion exchange MRIX (molecular species exchange) on the rare earth solution 11 after impurity removal, which is discharged from the ion exchange impurity removal system 9, for separating and extracting rare earth elements to obtain a high-purity rare earth product. A molecular recognition reagent 14 is added into the stirring tank 13 to form a rare earth complex solution 15 to identify the rare earth elements to be separated, and the rare earth complex solution 15 is sent to a molecular recognition ion exchange system 16 to separate the rare earth elements. As shown in FIG. 2, it can be known that although the properties of the rare earth elements are very similar, the atomic radii of each element are different, the difference depends on the elements to be separated, for example, the difference between neodymium and terbium is quite obvious, terbium and other metal impurities are respectively larger, and the molecular recognition is easier. Therefore, the molecular recognition is applied to the separation of rare earth waste materials of several rare earth elements, such as neodymium iron boron, rare earth dissolved salt electrolysis waste materials and the like, and has advantages.

The molecular recognition reagent 14 used in the present invention may be an organic complexing agent including tetraoxetane, tris [ N, N-bis (trimethylsilane) amine]Organic complexes such as; tetraoxetane (DOTA), a commonly used molecular recognition agent 14, is an organic compound, as shown in FIG. 3, which is relatively inexpensive and easy to synthesize, and has the chemical formula of (CH)₂CH₂NCH₂CO₂H）₄. The molecule consists of a central 12-membered tetraazacyclo 26, i.e., containing four nitrogen atoms. DOTA is used as complexing agent, especially for rare earth element ions 25. The tetraazacyclo 26 consisting of four nitrogen atoms can be modeled based on the size of the rare earth element 27 ion half, for example, the radius of the 3-valent terbium ion 25 is 92.3, and the DOTA complexing agent made according to the radius of the rare earth element 28 can capture the terbium ion 25 in the ionic state. The captured terbium-DOTA complex loses the state of 3-valent ions, and after the terbium-DOTA complex in the rare earth complex solution 15 is subjected to ion exchange by the molecular recognition ion exchange system 16, the terbium-DOTA complex is directly collected into a high-purity rare earth product 18 without being adsorbed.

When the molecular recognition agent is complexed to the rare earth element, the entire complex may be 1-2 or no ionic charge, tailored or modified depending on the application.

Other impurities adsorbed on the ion exchange can be washed out by a desorption agent and can be returned to the molecular recognition ion exchange system 16 for extraction or to the wastewater treatment system 19 for removing dirt, and the wastewater treated by the wastewater treatment system 19 can be returned to the ion exchange electrolytic membrane device 21 to be used as the reuse water 20 for manufacturing the reuse acid 5.

The invention can use inorganic acid, including hydrochloric acid, sulfuric acid or nitric acid, the acid concentration can be 5-35%; the invention can use inorganic alkali, including sodium hydroxide, sodium carbonate, ammonia water, potassium oxide, etc., with the concentration of 5-95%; the temperature of alkali dissolution and acid dissolution used in the invention can be from 5 to 150 ℃.

Example 1

The experiment is used for testing the recovery rate and the recovery purity of individual rare earth (praseodymium-neodymium) of a testing device, permanent magnet neodymium-boron waste materials are ground to 150 meshes and 200 meshes, then are roasted at 800 ℃ for two hours to form oxidation waste materials, the weight of the oxidation waste materials is 1Kg for testing, then 2 liters of 10 percent hydrochloric acid is used and heated at 80 ℃ for dissolving for 4 hours, the amount of the solution is maintained by evaporating water, then the pH is adjusted to 3-4 to remove partial impurities, and then the filtration and dehydration are carried out to obtain 2 liters of rare earth solution, wherein the assay content is as follows:

pumping 2L rare earth acid solution after pH adjustment into ion exchange purification resin, using amino phosphoric acid or weak acidic and weak alkaline corner resin of 2-aminomethyl pyridine functional group, making resin amount be 1L each, cleaning resin column with 500mmx800mm height, cleaning resin with acid and alkali before using, taking comprehensive sample to test concentration after passing resin, then adding prepared DOTA molecular identification agent to capture praseodymium and neodymium, then passing molecular identification ion exchange resin (strong acid type), making resin column with 500mmx800mm height, making resin amount be 1L, flow rate be 1L/h, cleaning resin with 1L of pure praseodymium, discharging to obtain 3L neodymium combined solution, precipitating with sodium carbonate, then cleaning with pure water, roasting to obtain neodymium oxide, testing neodymium oxide, making average praseodymium neodymium recovery rate be greater than 95%, obtaining high-purity neodymium oxide 99.99%, the results of the above assay are as follows:

example 2.

The experiment is used for testing the recovery rate of the dissolved salt electrolysis rare earth waste and the purity of the recovered terbium element generated when the device is used for processing the rare earth metal. Grinding the waste material to 150-mesh and 200-mesh, testing by using 1Kg of weight, adding 2 liters of 25% sodium carbonate and heating to 80 ℃ for alkali dissolution for 4 hours, mainly converting fluoride into soluble sodium fluoride, washing with water, filtering and dehydrating to obtain defluorinated slag, dissolving by using 2 liters of 10% sulfuric acid, heating to 80 ℃, keeping stirring for 4 hours, supplementing evaporated water to keep 2 liters of solution amount, adjusting pH to 3-4 to remove partial impurities, filtering and dehydrating to obtain 2 liters of rare earth solution, wherein the assay content is as follows:

pumping 2L rare earth acid solution after pH adjustment into ion exchange impurity removal resin, wherein the resin is weak acid coupling resin of iminodiacetic acid functional group, the resin amount is 1L, the resin column is 500mmx800mm high, the resin is cleaned by acid and alkali before use, 1L pure water is used for washing the resin after the resin is used, and a comprehensive sample (3L total) is taken for testing the concentration, then adding a customized DOTA molecular recognition medicament to capture terbium, then passing through a molecular recognition ion exchange resin (strong acid type), washing the resin with 1 liter of pure water after passing through a resin column with the height of 500mmx800mm and the resin amount of 1 liter and the flow rate of 1L/h, discharging to obtain 4 liters of praseodymium-neodymium combined solution, precipitating by using sodium carbonate, then, washing the product by pure water, roasting the product into terbium oxide, and then testing the purity of terbium oxide, wherein the average total rare earth recovery rate is more than 94%, thus obtaining the high-purity terbium oxide with the recovery rate of 99.5%, and the test results are as follows:

Claims

1. the utility model provides a retrieve device of tombarthite in follow tombarthite waste material, includes retort (10), solid-liquid separation equipment (6), ion exchange electrolytic membrane equipment (21), ion exchange edulcoration system (9), agitator tank (13) and molecular recognition ion exchange system (16), its characterized in that:

rare earth waste (1) and a dissolving agent are added into the reaction tank (10) to be dissolved and leached into a rare earth dissolved mixed solution (3), the rare earth dissolved mixed solution (3) is sent into a solid-liquid separation device (6) to separate a rare earth dissolved solution (8), the rare earth dissolved solution (8) is transferred into an ion exchange electrolytic membrane device (21) to separate a recycled acid (5) and a deacidified rare earth solution (24), and the recycled acid (5) returns to the reaction tank (10) for recycling; the deacidified rare earth solution (24) enters an ion exchange impurity removal system (9) to adsorb impurities (22) and separate an impurity-removed rare earth solution (11); feeding the rare earth solution (11) after impurity removal into a stirring tank (13), and then adding a molecular recognition reagent (14) and the rare earth solution (11) after impurity removal to mix to form a rare earth complex solution (15); the rare earth complex solution (15) is sent into a molecular recognition ion exchange system (16) for ion exchange, and then rare earth products (18) are separated.

2. The apparatus of claim 1, wherein: the apparatus further comprises a wastewater treatment system (19), the wastewater treatment system (19) treating the wastewater separated by the molecular recognition ion exchange system (16) into reuse water (20), and returning the reuse water (20) to the ion exchange electrolytic membrane device (21) for use in producing reuse acid (5).

3. The apparatus of claim 1, wherein: the dissolving agent comprises an alkaline dissolving agent and an inorganic acid dissolving agent, the alkaline dissolving agent is used for pretreatment of the rare earth waste (1), the rare earth waste (1) is subjected to dissolution pretreatment of the alkaline dissolving agent, is separated by a solid-liquid separation device (6), returns to the reaction tank (10), and is added with the inorganic acid dissolving agent for dissolution leaching.

4. The apparatus of claim 1, wherein: the reaction tank (10) further comprises a heating device (2), and when the dissolution leaching is carried out, the reaction tank (10) is heated to 5-150 ℃.

5. The apparatus of claim 4, wherein: the heating of the reaction tank (10) is 70-80 ℃.

6. The apparatus of claim 1, wherein: the ion exchange impurity removal system (9) adopts resin of iminodiacetic acid, aminophosphoric acid or 2-aminomethyl pyridine type.

7. The apparatus of claim 1 or 6, wherein: and after the ion exchange impurity removal system (9) is saturated with resin, desorption is carried out by adopting a desorption agent (29), and the eluted metal is recovered.

8. The apparatus of claim 1, wherein: the molecular recognition reagent (14) is tetraoxetane, tri [ N, N-bis (trimethylsilane) amine ] or other organic complexing agents.

9. The apparatus of claim 1 or 2, wherein: the dissolving agent is hydrochloric acid, sulfuric acid, nitric acid or other inorganic acids, and the acid concentration of the dissolving agent is 5-35%.

10. The apparatus of claim 1 or 2, wherein: the dissolving agent is sodium hydroxide, sodium carbonate, ammonia water, potassium oxyxide or other inorganic alkali, and the alkali concentration of the dissolving agent is 5-95%.